DE4034993A1 - New azo cpds., prepn. and use in dyeing - are chloro-di:fluoro-pyrimidinyl-amino benzoyl-amino sulpho-phenyl azo-hydroxy methyl sulpho-methyl-pyridone cpds. - Google Patents

Abstract

New 5-(4-(5-chloro -2,6-difluoro -pyrididin- 4-ylamino) benzoylamino) -1-sulphonphenyl -2-azo) -6-hydroxy-4 -methyl-sulphomethyl -pyrid-2-one cpds. (I) and their salts are of the formula (I). The R1 gps. independently = H or 1-4C alkyl, R2 = H 1-6C alkyl, 2-4C alkenyl, 2-4C alkynyl, cyclohexyl, phenyl, or phenyl-(1-4C alkyl) (in which the phenyl ring have 1-3 halogen, 1-4C alkyl, 1-4C alkoxy, -SO3H or -COOH substits) or 1-6C alkylene-Y, Y = -COOH, -COO-(1-4C alkyl) -SO3H, -OSO3H, -OH, -CN, 1-4C alkoxy, -NH2 or a protonisable (cyclo)aliphatic, aromatic or heterocyclic amino or quat. ammonium gp. (I) are prepd. by reacting the diazonium salt of a 5-((5-chloro-2,6-difluro pyrimidin-4-ylamino),benzoylamino-aniline -2-sulphonic acid with a 6-hydroxy-4-methyl -3-sulphomethyl -pyrid-2-one or a mixt. of these. ADVANTAGE - (I) are claimed for use in dyeing or printing organic substrates contg. OH gps. or N esp. fibrous materials consisting of or contg. natural or regenerated cellulose. They are also suitable for dyeing leather and natural or synthetic polyamides. (I) are reactive dyestuffs and combine well with other reactive dyestuffs. They give good exhaustion and fixing yields, whilst the unfixed dyestuff washed out well and the dyeing has good fastness.

Description

The invention relates to fiber-reactive monoazo compounds, processes for the production and their use as reactive dyes in dye and printing process.

The invention relates to compounds of the formula I.

and their salts, in which
R₁ independently represent hydrogen or C _1-4 alkyl, and
R₂ is hydrogen, C _1-6 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, cyclohexyl, phenyl or phenyl (C _1-4 alkyl), the phenyl ring of which is in each case unsubstituted or substituted by 1-3 Substituents from the series halogen, C _1-4 alkyl, C _1-4 alkoxy, -SO₃H and -COOH, or -C _1-6 alkylene-Y, wherein
Y denotes -COOH, -COOC _1-4 -alkyl, -SO₃H, -OSO₃H, -OH, -CN, C _1-4 -alkoxy, -NH₂ or a protonatable aliphatic, cycloaliphatic, aromatic or heterocyclic amino group or a quaternary ammonium group,
stand, as well as mixtures of compounds of formula I.

Unless otherwise stated, the definition includes alkyl, Alkenyl, alkynyl and alkylene both linear and branched radicals a.  

In the case of a hydroxy- or alkoxy-substituted alkyl or alkylene group, which is bound to nitrogen is the hydroxy or Alkoxy group preferred on a carbon atom that is not directly on nitrogen is bound.

Halogen generally means fluorine, chlorine or bromine; preferably chlorine or Bromine and especially chlorine.

R₁ is preferably hydrogen or methyl, especially hydrogen.

Y is preferably Y _a as -COOH, -SO₃H, -OSO₃H, -OH, -CN, methoxy, -NR₃R₄ or -⊕NR₅R₆R₇ An⊖, wherein
R₃ and R₄ independently of one another are hydrogen, unsubstituted C _1-4 -alkyl, by hydroxy, C _1-4 -alkoxy, -COOH, -SO₃H, -NHC _1-4 -alkyl or -N (C _1-4 -alkyl) ₂ monosubstituted C _1-4 alkyl, cyclohexyl which is unsubstituted or substituted by 1-3 methyl groups, phenyl or phenyl (C _1-4 alkyl), the phenyl ring of which is in each case unsubstituted or substituted by one or two groups from the halogen series , preferably chlorine, C _1-4 alkyl, C _1-4 alkoxy, -SO₃H and -COOH, or
-NR₃R₄ forms a piperidine, morpholine or piperazine ring, the latter may contain up to three methyl groups,
R₅ and R₆ independently of one another have the meanings of R₃ and R₄, but are independent of R₃ and R₄, with the exception of hydrogen, and
R₇ is C _1-4 alkyl or benzyl, or
-⊕NR₅R₆R₇ forms a pyridinium group, which may contain one or two methyl groups, and
An⊖ means a non-chromophoric anion.

More preferably Y is Y _b as -COOH, -SO₃H, -OSO₃H, -OH or -NR _3a R _4a , wherein
R _3a and R _4a independently of one another represent hydrogen, methyl, ethyl, 2-hydroxyethyl or phenyl (C _1-2 alkyl), or
-NR _3a R _4a forms a piperidine, morpholine or piperazine ring.

Y is particularly preferably Y _c as -OH, -SO₃H or -NR _3b R _4b , in which
R _3b and R _4b independently of one another are hydrogen, methyl or ethyl.
The anion An⊖ is preferably a chloride or acetate ion.

R₂ is preferably R _2a as hydrogen, methyl, ethyl, cyclohexyl, phenyl or phenyl (C _1-2 alkyl), the phenyl ring of which is unsubstituted or substituted by 1 or 2 substituents from the series chlorine, methyl, methoxy, -SO₃H and -COOH is, or as -C _1-4 alkylene Y _a . It is more preferably R _2b as hydrogen, methyl, ethyl, cyclohexyl, phenyl (C _1-2 alkyl) or -C _1-3 alkylene-Y _b . Most preferably it means R _2c as hydrogen, methyl, ethyl or - (CH₂) _n -Y _c , where n is 2 or 3.

Preferred compounds correspond to formula Ia

and their salts, wherein R _{2b is} as defined above.
Further preferred are compounds of the formula Ia in which R _{2b is} R _2c and R _{2c is} as defined above.

The nature of the cation of the sulfo groups and any additionally present carboxy groups in compounds of the formula I, if these are in salt form, is not a critical factor, but it can be any non-chromophoric cation which is customary in the chemistry of reactive dyes. However, the prerequisite is that the corresponding salts meet the condition of water solubility.
Examples of suitable cations are alkali metal ions or unsubstituted or substituted ammonium ions, such as, for example, lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.
Preferred cations are the alkali metal ions and ammonium, of which sodium is particularly preferred.

In general, in a compound of formula I, the cations of Sulfo groups and optionally carboxy groups are the same or different and be a mixture of the aforementioned cations, d. H. the compound can also be in mixed salt form.

The invention further comprises a process for the preparation of the compounds of formula I or mixtures thereof, characterized in that the diazonium salt of an amine of the formula II,

wherein R₁ is as defined above, or a mixture thereof, with a compound of formula III,

where R₂ is as defined above, or a mixture thereof.

The coupling of the diazonium compound of an amine of formula II to one Compound of the formula III is preferably added in an aqueous medium a pH around 7.

The compounds of formula II can be obtained by using a Compound of formula IV,

wherein R₁ is as defined above, with 5-chloro-2,4,6-trifluoropyrimidine implements.  

The condensation of a primary or secondary amino group Compound of formula IV with 5-chloro-2,4,6-trifluoropyrimidine preferably takes place at temperatures between 0 ° and 20 ° C and at pH from 3.0 to 8.0, preferably at pH 4.5-6.0.

The starting compounds of the formula III and IV are either known or they can be prepared analogously to methods known per se.

The compounds of the formula I can be isolated in a manner known per se; the compounds either precipitate by themselves or they can be separated from the reaction mixture, for example by customary salting out with alkali metal salts, filtered off and dried (in vacuo) at a slightly elevated temperature.
Depending on the reaction and isolation conditions, a compound of the formula I is obtained as a free acid or preferably in salt form or as a mixed salt and then contains, for example, one or more of the cations mentioned above. Salts or mixed salts can, however, also be prepared starting from the free acid in a conventional manner and vice versa, or a conventional salting-out process can also be carried out.

The compounds of formula I and mixtures thereof are reactive dyes dar; they are suitable for dyeing or printing hydroxy group or nitrogenous organic substrates. As preferred substrates These include leather and fiber materials made from natural or synthetic materials Polyamides and especially from natural or regenerated ones Cellulose, such as cotton, viscose or cellulose exist or contain them. The most preferred substrate is textile material made of cotton exists or contains them.

The compounds of the formula I can be used in dyeing liquors or in printing pastes by all dyeing or printing processes customary for reactive dyes be used. Preference is given to the pull-out process in the temperature range colored from 30-60 ° C.  

The compounds according to the invention can be used as a single dye or because of their good combinability also as a combination element with other reactive dyes of the same class, the comparable dye Properties e.g. B. regarding general fastness properties, extract value etc., are used. The combination stains obtained show just as good fastness properties as the dyeings with single dye.

With the compounds of the formula I, good extraction and fixing values are obtained. The unfixed dye can be easily washed out. The dyeings and prints obtained show good lightfastness. They also have good wet fastness properties such. B. with regard to washing, water, seawater and sweat fastness and have good resistance to oxidative influences such as chlorine-containing water, hypochlorite bleach, peroxide bleach and perborate-containing detergents.
Furthermore, the dyeings and prints show remarkable resistance to acid hydrolysis; For example, undiluted accompanying tissue is only slightly soiled when diluted acetic acid acts on the dye.

The following examples serve to illustrate the invention. In the Examples mean parts by weight or volume and percentages by weight. or volume percent; the temperatures are given in degrees Celsius.

example 1

68.4 parts of 3-amino-4 ′ - (5 ′ ′ - chloro-2 ′ ′, 6 ′ ′ - difluoropyrimidinylamino) -1-benzoylamine-topzole- 4-sulfonic acid are mixed in 600 parts of water. To 38 parts of aqueous 4N sodium nitrite solution are added. The received Suspension becomes 300 parts of ice and 45 for 60 minutes at 0-5 ° Parts of 30% hydrochloric acid added dropwise. The mixture is left for an hour Stirred 0-5 °, then the excess nitrite with little Sulphamic acid destroyed. Then 44.5 parts of 1-ethyl-6-hydroxy-4- are added  methyl-3-sulfomethylpyridone (2) dissolved in 500 parts of water. By Add 320 parts of 20% sodium carbonate solution to pH 7.0 posed. The yellow suspension becomes 450 parts of the dye Sodium chloride precipitated. The dye of the formula thus obtained

is filtered off and dried.
It dyes cotton in brilliant greenish yellow tones; the dyeings and prints on cotton obtained by customary methods show good wet fastness properties as well as good light fastness and are resistant to oxidative influences and to acid hydrolysis.

Examples 2-13

Analogous to the method described in Example 1 can be used using appropriate Starting materials other compounds of formula I prepared listed in the following table. They match of the formula (A)

for which the variables are listed in the table.
The compounds of Examples 2-13 can be used to dye or print substrates which consist of or contain cellulose fibers, and in particular textile materials made of cotton, by customary drawing and printing processes. The dyes listed in the table dye cotton in greenish yellow tones. The dyeings and prints obtained on cotton are good lightfast and wetfast and resistant to oxidative influences.

table

Compounds of formula (A)

According to the method described above, the dyes of Examples 1 to 13 obtained as sodium salts. You can be dependent from the chosen implementation and isolation conditions or by subsequent measures in a known manner in the form of free Acid or in another salt form or mixed salt form and then for example one or more of those in the description contain further cations.

Below are uses of the dyes described illustrated.  

Instructions for use A

In a dyebath containing 0.3 parts in 300 parts of demineralized water of the dye from Example 1 and 15 parts of Glauber's salt (calcined) contains, 10 parts of cotton fabric (bleached) are entered at 40 °. After 30 minutes at 40 °, the addition is carried out at intervals of 10 minutes of a total of 6 parts of soda (calcined) in 0.2 portions; 0.6; 1,2 and finally 4 parts, keeping the temperature at 40 ° becomes. The dyeing is then continued at 40 ° for one hour. Subsequently the dyed material is left in flowing cold for 3 minutes Water, then rinsed in running hot water for 3 minutes. The coloring is in 15 parts in 500 parts of demineralized water in the presence 0.25 parts of Marseille soap is boiled. After rinsing in running water (hot for 3 minutes), centrifuge and stain dried in a drying cabinet at approx. 70 °. You get a greenish tinge yellow cotton dyeing of good fastness properties, especially good ones Light and wet fastness shows and is stable against oxidative influences.

Application regulation B

10 parts of cotton material (bleached) are added to a dyebath containing 10 parts of Glauber's salt (calcined) in 300 parts of demineralized water. The bath is heated to 40 ° within 10 minutes, then 0.5 part of the dye from Example 1 is added. After a further 30 minutes at 40 °, 3 parts of soda (calcined) are added, followed by dyeing at 40 ° for a further 45 minutes.
The dyed material is rinsed with running cold water, then with hot water and washed boiling analogously to that described for regulation A. After rinsing and drying, a greenish yellow cotton dyeing is obtained which has the properties listed for regulation A.

The dyes can also be used in the same way as described in regulations A and B. of Examples 2-13 or mixtures of the dyes from the Examples 1-13 can be used for dyeing. The greenish yellow cotton dyeings obtained have good fastness properties.  

Instructions for use C

A printing paste with the ingredients

40 parts of the dye from Example 1
100 parts of urea
350 parts of water
500 parts of a 4% sodium alginate thickener
10 parts of sodium bicarbonate
1000 pieces in total

is applied to cotton material using the usual printing processes.

The printed material is steamed at 102-104 ° for 4-8 minutes and then rinsed cold and hot. Then the fixed cotton material washed at the boil (analogous to regulation A) and dried. The received one greenish yellow print shows good general fastness properties.

Analogously to regulation C, the dyes of Examples 2-13 or dye mixtures from Examples 1-13 for printing on Cotton are used. In all cases, greenish tones become yellow Obtain prints with good fastness properties.

Claims (10)

1. Compounds of formula I. and their salts, in which
R₁ independently represent hydrogen or C _1-4 alkyl, and
R₂ is hydrogen, C _1-6 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, cyclohexyl, phenyl or phenyl (C _1-4 alkyl), the phenyl ring of which is unsubstituted or substituted by 1-3 Substituents from the series halogen, C _1-4 alkyl, C _1-4 alkoxy, -SO₃H and -COOH, or -C _1-6 alkylene-Y, wherein
Y denotes -COOH, -COOC _1-4 -alkyl, -SO₃H, -OSO₃H, -OH, -CN, C _1-4 -alkoxy, -NH₂ or a protonatable aliphatic, cycloaliphatic, aromatic or heterocyclic amino group or a quaternary ammonium group,
stand, as well as mixtures of compounds of formula I. 2. Compounds according to claim 1, wherein Y is Ya and Ya is -COOH, -SO₃H, -OSO₃H, -OH, -CN, methoxy, -NR₃R₄ or -⊕NR₅R₆R₇ An⊖, wherein
R₃ and R₄ independently of one another are hydrogen, unsubstituted C _1-4 -alkyl, by hydroxy, C _1-4 -alkoxy, -COOH, -SO₃H, -NHC _1-4 -alkyl or -N (C _1-4 -alkyl) ₂ monosubstituted C _1-4 alkyl, cyclohexyl which is unsubstituted or substituted by 1-3 methyl groups, phenyl or phenyl (C _1-4 alkyl), the phenyl ring of which is in each case unsubstituted or substituted by one or two groups from the halogen series , C _1-4 alkyl, C _1-4 alkoxy, -SO₃H and -COOH, stand or
-NR₃R₄ forms a piperidine, morpholine or piperazine ring, the latter may contain up to three methyl groups,
R₅ and R₆ independently of one another have the meanings of R₃ and R₄, but independently of R₃ and R₄, except hydrogen, and
R₇ is C _1-4 alkyl or benzyl, or
-⊕NR₅R₆R₇ forms a pyridinium group, which may contain one or two methyl groups, and
An⊖ means a non-chromophoric anion. 3. Compounds according to claim 2, wherein R₂ is R _2a and R _{2a is} hydrogen, methyl, ethyl, cyclohexyl, phenyl or phenyl (C _1-4 alkyl), wherein each phenyl ring is unsubstituted or substituted by one or two substituents from the Row means chlorine, methyl, methoxy, -SO₃H and -COOH, or -C _1-4 alkylene-Y _a , wherein Y _{a is} as defined in claim 2. 4. Compounds according to any one of claims 1-3, wherein each R₁ Means hydrogen. 5. Compounds according to claim 1, which of the formula Ia and salts thereof, wherein
R _2b for hydrogen, methyl, ethyl, cyclohexyl, phenyl (C _1-4 alkyl) or -C _1-3 alkylene-Y _b , and
Y _{b represents} -COOH, -SO₃H, -OSO₃H, -OH or -NR _3a R _4a , in which
R _3a and R _4a independently of one another are hydrogen, methyl, ethyl, 2-hydroxyethyl or phenyl (C _1-2 -alkyl) or -NR _3a R _4a forms a piperidine, morpholine or piperazine ring. 6. Compounds according to claim 5, wherein R _{2b is} R _2c and R _{2c is} hydrogen, methyl, ethyl or - (CH₂) _n -Y _c , wherein n is 2 or 3 and Y _{c is} -OH, -SO₃H or - NR _3b R _4b are in which R _3b and R _4b independently of one another are hydrogen, methyl or ethyl. 7. A process for the preparation of compounds of the formula I, defined in claim 1, or mixtures thereof, characterized in that the diazonium salt of an amine of the formula II, wherein R₁ is as defined in claim 1, or a mixture thereof, with a compound of formula III, wherein R₂ is as defined in claim 1, or a mixture thereof. 8. Process for dyeing or printing hydroxy groups or nitrogenous organic substrates, characterized in that one with a compound according to any one of claims 1-6, or with mixtures of which colors or prints. 9. The method according to claim 8, for dyeing or printing fiber materials, which consist of natural or regenerated cellulose or these contain. 10. The dyed or printed substrates according to claim 8 and 9.